Vegetable oil based polyols and polyurethanes made therefrom

ABSTRACT

Polyols useful in the manufacture of polyurethanes are disclosed. The polyols are prepared by reacting a vegetable oil based (hydroxymethyl containing) monomer with a polyol, polyamine or aminoalcohol under vacuum.

FIELD OF THE INVENTION

The invention relates to improved methods of making vegetable basedpolyols to make, for example, polyurethane foams.

BACKGROUND OF THE INVENTION

Polyurethanes are produced by the reaction of polyisocyanates andpolyols. The first large scale commercial production of polyurethanesarose using polyester polyols from the ester condensation reaction ofdiols or polyols and dicarboxylic acids to make flexible foams. Thepolyester polyols were supplanted by polyether polyols because of lowercost and ability to make a wide range of polyols. Polyethers are made bypolymerizing epoxides (oxiranes) derived from petroleum feedstocks withactive hydrogen starting compounds (polyols and polyamines).

Rigid polyurethane foams have been made with castor oil or castor oilbyproducts. Castor oil has been used in rigid foams because of its lowmolecular weight (short chain length) and high functionality(trihydroxyl).

Attempts have been made to make polyols from vegetable or renewablefeedstocks such as those disclosed by Peerman et al., U.S. Pat. Nos.4,423,162; 4,496,487 and 4,543,369. Peerman et al. describe a methodreacting a hydroxyester monomer with a polyol or polyamine. However,Peerman et al., specifically describe problems of gelling, which can beavoided by limiting the extent of conversion or by using quantities ofreactants far from the amounts required stoichiometrically.Consequently, Peerman et al., only describe elastomers (crosslinkedrigid polyurethanes) from their resultant polyols. In addition, thepresence of secondary hydroxyls were described as causing sweating,wherein the product appears to be wet and not fully cured, thus limitingthe use of low cost renewable initiators such as glycerol.

Accordingly, it would be desirable to provide both a formation methodand a vegetable based polyol that solves one or more of the problems ofthe prior art, such as one of those described above. In particular itwould be desirable to provide a vegetable oil based (VOB) polyol thatcan be used to make flexible polyurethane foams in the absence of anyother polyols.

SUMMARY OF THE INVENTION

A first aspect of the invention is a process to make a vegetable oilbased polyol, the process comprising,

-   -   i) mixing an initiator that is a polyol, polyamine, aminoalcohol        or mixture thereof and a vegetable oil based (VOB) monomer        having at least one of the formulae:    -   where m, n, v, r, and s are integers and m is greater than 3, n        greater than or equal to zero and m+n is from 11 to 19, v is        greater than 3, r is greater than or equal to zero, s is greater        than or equal to zero and v+r+s is from 10 to 18, and    -   ii) heating the mixture to a reaction temperature, for a        reaction time, while under a vacuum and in the presence of an        amount of catalyst sufficient to form the vegetable oil based        polyol. It is understood that the initiator fails to contain an        ester group that can transesterify under the reaction        conditions.

The method of the first aspect surprisingly may form a non-gelled polyolwith sufficient hydroxyl functionality and molecular weight to form aflexible foam when reacted with a polyisocyanate. The process eventhough performed under vacuum may use initiators that would volatilizeoff relative quickly at the reaction temperature used to form the VOBpolyol. The process, surprisingly, makes novel non-gelled VOB polyolseven when VOB monomers are present that have three hydroxyl groups.Finally, it has been surprisingly found that the process forms a uniqueVOB polyol, where all of the VOB monomer is reacted, but within thepolyol there are some hydroxyl or amine groups of the initiator thathave not been reacted even though the amount of VOB monomer is far inexcess of the stoichiometric amount needed to react therewith.

A second aspect of the invention is a process to make a vegetable basedpolyol, the process comprising,

-   -   i) heating, in the presence of a catalyst a vegetable oil based        monomer having at least one of the formulae:    -   where m, n, v, r, and s are integers and m is greater than 3, n        greater than or equal to zero and m+n is from 11 to 19, v is        greater than 3, r is greater than or equal to zero, s is greater        than or equal to zero and v+r+s is from 10 to 18 until some        portion of the VOB monomers have reacted and subsequently    -   ii) introducing an initiator that is a polyol, polyamine,        aminoalcohol or mixture thereof to the reacted VOB monomers of        step (i) for a time and temperature, under vacuum, sufficient to        form the vegetable based polyol. This aspect of the invention        has been found to surprisingly make similar VOB polyols even        though the initiator is added after the VOB monomers have, for        example, built substantial molecular weight. The method is        believed to give improved control over the resultant molecular        weight of the VOB polyol that is formed.

A third aspect of the invention is a vegetable oil based polyolcomprised of

where R is a residue of a polyol, polyamine or aminoalcohol initiator; Xand X′ may the same or different and is O, N or NH; p is an integer from1 to 5; q is an integer from 1 to 5 wherein p+q is from 3 to 8, t is aninteger from 3 to 8 and A may be the same or different and is selectedfrom the group consisting of A1, A2 and A3 where

where m, n, v, r, s, a, b and c are integers and m is greater than 3, ngreater than or equal to zero and m+n is from 11 to 19, v is greaterthan 3, r is greater than or equal to zero, s is greater than or equalto zero and v+r+s is from 10 to 18, a is from 0 to 35, b is from 0 to 35and c is from 0 to 35, so long as that all a's, b's and c's in anymolecule of the vegetable oil based polyol are not all zero and(a+b+c)/(p+q+t) is about 5 to about 100 in the vegetable oil basedpolyol. It is understood that each or all of the hydroxyls may reactwith the methyl ester of another VOB monomer. As such, it is understoodthat the structures shown above merely model the actual degree ofreaction (i.e., one VOB monomer hydroxyl reacted). However, any or allof the available hydroxyl groups are capable of reacting under theconditions of the polymerization. That is to say, the growth of thechain may occur not only at the hydroxyl site depicted in the abovestructures, but, at any of the hydroxyls of the VOB monomer. It is alsoconceivable that more than one of the available hydroxyl groups of theVOB monomer may be acylated.

A fourth aspect of the invention is a vegetable oil based polyolcomprised of

where R is a residue of a polyol, polyamine or aminoalcohol initiator; Xand X′ may be the same or different and is O, N or NH; p is an integerfrom 1 to 5; q is an integer from 1 to 5 wherein p+q is from 2 to 8, tis an integer from 2 to 8 and A may be the same or different and isselected from the group consisting of A1, A2 and A3 where

where m, n, v, r, s, a, b and C are integers and m is greater than 3, ngreater than or equal to zero and m+n is from 11 to 19, v is greaterthan 3, r is greater than or equal to zero, s is greater than or equalto zero and v+r+s is from 10 to 18, a is from 0 to 35, b is from 0 to 35and c is from 0 to 35, so long as that all a's, b's and c's areessentially not all zero, at least a portion of A is A3 and(a+b+c)/(p+q+t) is greater than 0 to about 100 in the vegetable oilbased polyol.

The vegetable oil based polyols may be used in any applications thatpolyols are used. Examples include polyurethane applications of alltypes such as elastomers, coatings, adhesives, sealants, rigid foams andin particular flexible foams.

DETAILED DESCRIPTION OF THE INVENTION

The vegetable based polyols of the present invention are made byreacting an initiator with a vegetable oil based (VOB) monomer. Theinitiator has at least one active hydrogen, which are reacted with theVOB monomer. The initiator may be depicted by the formula:R(XH)_(p)Where X is O, N, or NH and p is 1 to 8. In the formula, X may be thesame or different. The initiator therefore encompasses polyols,polyamines and aminoalcohols. R generally represents a linear, cyclicchain or combination thereof of alkane (C—C), alkene (C═C), ether(C—O—C) linkages or combinations thereof. The carbons within theaforementioned chain may be substituted with a methyl or ethyl group.Generally the molecular weight of the initiator is at most from 32 toabout 2000. Preferably, the molecular weight is at least about 50, morepreferably at least about 60, most preferably at least about 90 topreferably at most about 1400, more preferably at most about 1200 andmost preferably at most about 800.

Exemplary polyol initiators include neopentylglycol; 1,2-propyleneglycol; trimethylolpropane; pentaerythritol; sorbitol; sucrose;glycerol; alkanediols such as 1,6-hexanediol; 2,5-hexanediol;1,4-butanediol; 1,4-cyclohexane diol; ethylene glycol; diethyleneglycol; triethylene glycol; 9(1)-hydroxymethyloctadecanol,1,4-bishydroxymethylcyclohexane;8,8-bis(hydroxymethyl)tricyclo[5,2,1,0^(2,6)]decene; Dimerol alcohol (36carbon diol available from Henkel Corporation); hydrogenated bisphenol;9,9(10,10)-bishydroxymethyloctadecanol; 1,2,6-hexanetriol; any of theaforementioned where at least one of the alcohol or amine groups presenttherein has been reacted with ethylene oxide, propylene oxide or mixturethereof; and combination thereof.

Any of the aforementioned where at least one of the alcohol groupspresent therein has been reacted with ethylene oxide or propylene oxidemeans the active hydrogen of the hydroxyl reacts to form a polyetherpolyol exemplified by the following formula:

where R is the same as defined above. It is also understood that theother alkoxylating agents instead of ethylene oxide or propylene oxidemay be. Amine groups may also be reacted with the alkoxylating agent.

Exemplary polyamine initiators include ethylene diamine;neopentyldiamine, 1,6-diaminohexane; bisaminomethyltricyclodecane;bisaminocyclohexane; diethylene triamine; bis-3-aminopropyl methylamine;and triethylene tetramine.

Exemplary aminoalcohols include ethanolamine, diethanolamine, andtriethanolamine.

Other useful initiators that may be used include polyols, polyamines oraminoalcohols described in U.S. Pat. Nos. 4,216,344; 4,243,818 and4,348,543 and British Pat. No. 1,043,507.

Preferably, the initiator is selected from the group consisting ofneopentylglycol; trimethylolpropane; pentaerythritol; sorbitol; sucrose;glycerol; 1,2-propylene glycol; 1,6-hexanediol; 2,5-hexanediol;1,6-hexanediol; 1,4-cyclohexane diol; 1,4-butanediol; ethylene glycol;diethylene glycol; triethylene glycol; bis-3-aminopropyl methylamine;ethylene diamine; diethylene triamine; 9(1)-hydroxymethyloctadecanol;1,4-bishydroxymethylcyclohexane;8,8-bis(hydroxymethyl)tricyclo[5,2,1,0^(2,6)]decene; Dimerol alcohol;hydrogenated bisphenol; 9,9(10,10)-bishydroxymethyloctadecanol;1,2,6-hexanetriol; any of the aforementioned where at least one of thealcohol or amine groups present therein has been reacted with ethyleneoxide, propylene oxide or mixture thereof; and combination thereof.

More preferably the initiator is selected from the group consisting ofneopentylglycol; 1,2-propylene glycol; trimethylolpropane;pentaerythritol; ethoxylated pentaerythritol; propoxylatedpentaerythritol; sorbitol; sucrose; glycerol; ethoxylated glycerol;propoxylated glycerol; diethanolamine; alkanediols such as1,6-hexanediol, 1,4-butanediol; 1,4-cyclohexane diol; 2,5-hexanediol;ethylene glycol; diethylene glycol, triethylene glycol;bis-3-aminopropyl methylamine; ethylene diamine; diethylene triamine;9(1)-hydroxymethyloctadecanol, 1,4-bishydroxymethylcyclohexane;8,8-bis(hydroxymethyl)tricyclo[5,2,1,0^(2,6)]decene; Dimerol alcohol;hydrogenated bisphenol; 9,9(10,10)-bishydroxymethyloctadecanol;1,2,6-hexanetriol and combination thereof.

Even more preferably the initiator is selected from the group consistingof glycerol; ethylene glycol; 1,2-propylene glycol; trimethylolpropane;ethylene diamine; pentaerythritol; diethylene triamine; sorbitol;sucrose; or any of the aforementioned where at least one of the alcoholor amine groups present therein has been reacted with ethylene oxide,propylene oxide or mixture thereof; and combination thereof.

Most preferably the initiator is glycerol, pentaerythritol, sucrose,sorbitol, an ethoxylated glycerol, propyxylated glycerol, ethoxylatedpentaerthritol, propyxylated pentaerthritol or mixture thereof.

Surprisingly, using the method of the present invention, it is preferredthat an initiator is used that has at least one secondary hydroxyl orsecondary amine (e.g., glycerol). It is surprising, because the reactionmay cause the VOB monomer to react, for example with glycerol, in such away that the resultant vegetable oil based polyol has at least somepolyol molecules where at least one of the primary hydroxyls of theglycerol has not reacted with the VOB monomer, but thesecondary-hydroxyl has. This is further described below.

The VOB monomer is a vegetable oil based monomer having at least one ofthe formulae:

where m, n, v, r, and s are integers and m is greater than 3, n greaterthan or equal to zero and m+n is from 11 to 19, v is greater than 3, ris greater than or equal to zero, s is greater than or equal to zero andv+r+s is from 10 to 18.

The VOB monomer may be of any animal fat or vegetable oil that iscomprised of triglycerides that upon saponification with a base such asaqueous sodium hydroxide yields a fatty acid and glycerol, where atleast a portion of the fatty acids are unsaturated fatty acids (i.e.,contain at least one carbon double bond). Preferred vegetable oils arethose that yield at least about 70 percent unsaturated fatty acids byweight. More preferably, the vegetable oil yields at least about 85percent, more preferably at least 87 percent, and most preferably atleast about 90 percent by weight unsaturated fatty acids. It isunderstood that specific fatty acids derived from a vegetable oil,animal fat or any other source may be used. That is to say, for example,palmitoleic, oleic, linoleic, linolenic and arachidonic fatty acid alkylesters may be used to form the VOB monomer directly. It is preferred,however, to use a vegetable oil as previously described. Preferredvegetable oils include, for example, soy, safflower, cotton, linseed,peanut, olive, sunflower, canola, rapeseed, corn, palm oil orcombination thereof. More preferably, the vegetable oil is a soy,sunflower, canola, corn, rapeseed oil, or combination thereof. Mostpreferably, the vegetable oil is soy, sunflower, canola oil orcombination thereof. It is understood that the vegetable oil may beobtained from a genetically modified organism, such as geneticallymodified soybean, sunflower or canola.

The unsaturated fatty acid alkyl esters then may be formed, by anysuitable process such as those known in the art, into the VOB monomer(hydroxymethylesters). For example, the hydroxymethyl group may beintroduced by a hydroformylation process using a cobalt or rhodiumcatalyst followed by the hydrogenation of the formyl group to obtain thehydroxymethyl group by catalytic or by chemical reduction. Procedures toform the hydroxymethylesters are described in U.S. Pat. Nos. 4,216,343;4,216,344; 4,304,945 and 4,229,562 and in particular 4,083,816. Otherknown processes to form hydroxymethylesters from fatty acids may also beused such as described by U.S. Pat. Nos. 2,332,849 and 3,787,459.

In forming the VOB monomers, the formylated fatty acid alkyl esters maybe completely formylated or only partially formylated. That is to say,the fatty acid alkyl esters of the particular vegetable oil may havesome remaining unsaturated (C═C) bonds. Preferably, however, the amountof unsaturated bonds remaining after formylation is as described inconcurrently filed application titled “ALDEHYDE AND ALCOHOL COMPOSITIONSDERIVED FROM SEED OILS,” having inventors Donald Morrison et al.,attorney docket number 63104, and U.S. Provisional Application No.60/465,663, filed Apr. 25, 2003 and concurrently filed non-provisionalapplication claiming priority therefrom, incorporated herein byreference. After the fatty acid alkyl esters are formylated they arehydrogenated, such that there is desirably essentially no remainingunsaturated bonds (i.e., trace amounts at most and preferably nodetectable amounts of unsaturation).

The VOB monomer and the initiator are mixed or blended together by anysuitable means such as those known in the art. For example, simplestirring is sufficient.

The VOB monomer and initiator are heated to a reaction temperature, fora reaction time, while under a vacuum and in the presence of an amountof a catalyst sufficient to form the vegetable based polyol. Thereaction temperature that is employed is, for example, a function of theVOB monomer, initiator and catalyst, but the reaction temperature isgenerally at least about 140° C. to about 300° C. when using a tin ortitanium catalyst. Preferably, the reaction temperature is at leastabout 150° C., more preferably at least about 180° C., most preferablyat least about 190° C. to preferably at most about 250° C., morepreferably at most about 220° C. and most preferably at most about 210°C.

The catalyst may be any suitable catalyst such as a tin, titanium,enzyme catalyst (e.g., lipase), carbonate catalyst (e.g., K₂CO₃, NaHCO₃)or combination thereof.

In a preferred embodiment, the catalyst is an enzyme catalyst, such aslipase, which allows the reaction temperature to be below about 100° C.to about room temperature. This in turn allows the use of initiators(e.g., sugar) that would be degraded by the higher temperatures usingtin or titanium catalysts.

The reaction time, similarly, is dependent on the variables describedabove for the reaction temperature. Generally, the time is at leastabout 10 minutes to at most about 24 hours. Preferably, the reactiontime is at least about 15 minutes, more preferably at least about 30minutes, more preferably at least about 1 hour to preferably at mostabout 12 hours, more preferably at most about 9 hours and mostpreferably at most about 5 hours.

To form the VOB polyol, it has been found that it is critical that thereaction be carried out under a vacuum. This is even true where theinitiator is volatile at the reaction temperature. Volatile means thatthe initiator will volatilize off entirely in substantially less timethan the total reaction time under the vacuum. For example, when theinitiator is glycerol, the glycerol in the reaction vessel minus the VOBmonomer would be volatilized off under a vacuum of about 20 torr inabout 120 minutes at 200° C. Generally, the vacuum is at least about 100torr. Preferably the vacuum is at least about 50 torr, more preferablythe vacuum is at least about 20 torr.

In a preferred embodiment, particularly when using a volatile initiator,the VOB is placed in the reactor under vacuum at the reactiontemperature for a period of time sufficient to transesterify asubstantial amount of the VOB monomer (e.g., at least about 10 percentof the ester groups of the VOB monomer have undergonetransesterification) and subsequently the initiator is added to form theVOB polyol. This method allows for precise control of the molecularweight without substantial loss of a volatile initiator.

The amount of catalyst has also been found to be critical when using atin or titanium catalyst solely. This is particularly true when theinitiator is volatile as described previously. The amount of catalystmust be some minimum amount to effect the reaction between the initiatorand VOB monomer sufficiently quickly to realize the VOB polyol. Theamount of catalyst depends, for example, on the particular type ofcatalyst, VOB monomer, and initiator.

Generally, when a tin catalyst is employed, the amount of catalyst is atleast about 100 ppm to at most about 2500 ppm by weight of tin to thetotal reaction mixture. Preferably, the amount of tin catalyst is atleast about 250 ppm, more preferably at least about 500 ppm and mostpreferably at least about 1000 ppm to preferably at most about 2000 ppm,more preferably at most about 1500 ppm. The tin catalyst may be anysuitable tin catalyst such as those known in the art. Exemplary tincatalysts include tin (II) octanoate, tin (II) 2-ethylheptanoate,dibutyl tin (IV) dilaurate, and other tin catalysts which are similarlyfunctionalized. Preferably the tin catalyst is tin (II) octanoate, tin(II) 2-ethylheptanoate, dibutyl tin (IV) dilaurate or combinationthereof.

Generally, when a titanium catalyst is employed, the amount of catalystis at least about 100 ppm to at most about 2500 ppm by weight oftitanium to the total reaction mixture. Preferably, the amount oftitanium catalyst is at least about 250 ppm, more preferably at leastabout 500 ppm and most preferably at least about 1000 ppm to preferablyat most about 2000 ppm, more preferably at most about 1500 ppm. Thetitanium catalyst may be any suitable such as those known in the art.Exemplary titanium catalysts include titanium tetraisopropoxide,titanium tetraisobutoxide, or any appropriately functionalized titanium(IV) alkoxide. Preferably the titanium catalyst is titaniumtetraisopropoxide.

The ratio of VOB monomer to initiator reactive groups is typically atleast a stoichiometric amount (i.e., if the initiator is 1 mole ofglycerol, the amount of VOB monomer is at least 3 moles) to at mostabout 100. Preferably the ratio of VOB monomer to initiator reactivegroups is at least 2, more preferably at least about 5, even morepreferably at least about 7 and most preferably at least about 10, topreferably at most about 50, more preferably at most about 25, and mostpreferably at most about 20. It has been surprisingly found when usingthese higher ratios even when reacting with a VOB monomer havingmultiple hydroxy group monomers therein a VOB polyol may be formed thatis non-gelled and even a liquid.

When employing the method of the present invention, it has beensurprisingly discovered that a VOB polyol may be formed that has atleast a portion of the polyol being comprised of a polyol molecule thathas at least one initiator reactive group that is unreacted even whilethe VOB polyol as a whole has a VOB monomer to initiator reactive siteratio of at least 5. That is to say, the VOB polyol is comprised of

where

R is a residue of a polyol, polyamine or aminoalcohol initiator;

X and X′ may be the same or different and is O, N or NH; p is an integerfrom 1 to 5; q is an integer from 1 to 5 wherein p+q is from 3 to 8, tis an integer from 3 to 8 and A may be the same or different and isselected from the group consisting of A1, A2 and A3 where

where m, n, v, r, s, a, b and c are integers and m is greater than 3, ngreater than or equal to zero and m+n is from 11 to 19, v is greaterthan 3, r is greater than or equal to zero, s is greater than or equalto zero and v+r+s is from 10 to 18, a is from 0 to 35, b is from 0 to 35and c is from 0 to 35, so long as that all a's, b's and c's in anymolecule of the vegetable oil based polyol are not all zero and(a+b+c)/(p+q+t) is about 5 to about 100 in the vegetable oil basedpolyol. The (a+b+c)/p+q+t) ratio is indicative of the VOB monomer toinitiator reactive group ratio.

In a preferred embodiment, the VOB polyol has at least a portion of thepolyol being comprised of A3 constituent. This particular embodiment ispreferred, because, it allows the polyol to realize a sufficienthydroxyl functionality while achieving a sufficient molecular weight foruse to make, for example, flexible polyurethane foams using the VOBpolyol as the sole polyol reacted with an isocyanate to form thepolyurethane foam. Preferably, the amount of the A3 constituent in theVOB polyol is at least about 0.01 weight percent of the total VOBpolyol, more preferably the amount is at least about 0.02 weightpercent, most preferably at least about 0.05 weight percent topreferably at most about 25 weight percent, more preferably at mostabout 20 weight percent and most preferably at most about 10 weightpercent of the VOB polyol.

When the VOB polyol contains A3, (a+b+c)/(p+q+t) is greater than 0 toabout 100. Preferably, (a+b+c)/(p+q+t) is at least about 0.25, morepreferably at least about 0.5, most preferably at least about 1, topreferably at most about 50, more preferably at most about 25 and mostpreferably at most about 20.

In another preferred embodiment when employing an initiator having, forexample, a secondary hydroxyl or amine, the VOB polyol may have aportion of the VOB polyol that has a structure

where at least one X′—H group is a primary hydroxyl or primary amine andat least one X-A-H is located at a position corresponding to a secondaryhydroxyl or secondary amine of the initiator. Preferably, the VOB polyolis at least partially comprised of the above structure where all of theX′—H groups are a primary hydroxyl or primary amine and all of the X-A-Hgroups are located at a position corresponding to a secondary hydroxylor secondary amine of the initiator.

The VOB polyol may be used to make polyurethanes by reacting it with apolyisocyanate such as those known in the art using known methods tomake such polyurethanes. Preferably the polyurethane is a flexible foam.More preferably the polyurethane is a flexible foam that has been formedby reacting the VOB polyol with a polyisocyanate in the absence of anyother polyol. That is to say the VOB polyol is the sole polyol that isused to make the flexible foam.

Generally the VOB polyol may have a weight average molecular weight ofabout 350 to about 10,000. Preferably the weight average molecularweight is at least about 500, more preferably at least about 1000 andmost preferably at least about 1200 to preferably at most about 10,000,more preferably at most about 6000 and most preferably at most about3000. It is preferred that the VOB polyol is a liquid and surprisinglythe method employed is capable of making high molecular weight polyolswithout gellation.

VOB polyols of the invention may be used with any of the additivescommonly known in the art for the production of polyurethane polymers.Any of a range of additives such as blowing agents, catalysts,surfactants, cell openers, colorants, fillers, load bearing enhancementadditives such as copolymer polyols, water, internal mold releases,antistatic agents, antimicrobial agents, and other additives known tothose skilled in the art are useful within the scope of the invention.

While the full range of surfactants which are typically used in theformation of polyurethane foams are useful, certain surfactants arepreferred for foams which have high percentages of vegetable basedpolyols as the polyol component of the foam formulation. In particular,in the formation of flexible slabstock foam, high efficiencyalkoxylsilane surfactants such as those commonly used in specialtygrades of flexible foam such as low-resiliency or “visco-elastic” foamare unexpectedly found to greatly enhance the properties of flexibleslabstock foams made when 100 percent of the polyol side of the foam ismade from VOB polyol. Surfactants which are preferred are those such asL626 available from Crompton Corporation or other polyol pendant chainsgrafted with a silicone moiety. Property enhancements are observed inproperties such as foam cell size, cell structure, foam feel or “hand,”which is defined as the aesthetic feel or tactile quality of the foam,that indicates its fineness, texture, and durability, and foam porosity.The preferred surfactants result in slabstock foam products from 100percent VOB polyol which have such properties comparable to slabstockfoams prepared from 100 percent conventional commercial-grade EO/POpolyols.

It also has been found that the VOB polyols of this invention may formpolyurethane foams made with a wide range of water concentrations.Generally, the water concentrations may range from about 1 part perhundred parts to about 10 parts per hundred parts of polyol by weight.Preferably, the water concentration is at least about 2, more preferably3 and most preferably at least about 4 to preferably at most about 9,more preferably at most 8 and most preferably at most about 6 parts perhundred parts of polyol by weight.

EXAMPLES Examples 1-27 Methods for Producing Polyols from Vegetable OilBased Fatty Acid Methyl Esters

Hydroxymethylated fatty acid methyl esters of soybean oil and9,(10)-hydroxymethyl stearate (from methyl oleate) are producedaccording to the procedure described in concurrently filed applicationtitled “ALDEHYDE AND ALCOHOL COMPOSITIONS DERIVED FROM SEED OILS,”having inventors Donald Morrison, et al., attorney docket number 63104described previously.

Glycerol was obtained from the Sigma-Aldrich Chemical Company (CAS#[56-81-51) and distilled under vacuum at 20 mm/183° C. Distilledglycerol was then stored under nitrogen until used.

CEI-625 is a glycerol initiated EO polyol with a number averagemolecular weight of 625. It is produced at The Dow Chemical Company.

Trimethylolpropane [77-99-6] is obtained from the Sigma-Aldrich ChemicalCo.

1,6-hexanediol [629-11-8] is obtained from the Sigma-Aldrich ChemicalCo.

CEI-1200 is a glycerol initiated EO polyol with a number averagemolecular weight of 1200. It is produced at The Dow Chemical Company.

PE-270 is a pentaerythritol based polyol which has been ethoxylated withethylene oxide to a number average molecular weight of 270. PE-270 isavailable from Aldrich Chemical Company of Milwaukee, Wis.

Tetrol 600 is pentaerythritol which has been ethoxylated to a numberaverage molecular weight of 600. It was prepared at The Dow Chemical Co.

Tetrol 800 is pentaerythritol which has been ethoxylated to a numberaverage molecular weight of 800. It is available from Sigma AldrichChemical Company of Milwaukee, Wis., and is sold as pentaerythritolethoxylate (30599-15-6].

Sucrose [57-50-1] is obtained from the Imperial Sugar Co.

D-Sorbitol [50-70-4] is obtained from the Sigma Aldrich Chemical Co.

Pentaerythritol [115-77-5] is obtained from the Sigma Aldrich ChemicalCo.

N-methylpyrrolidinone (NMP) [872-50-4] is obtained from the SigmaAldrich Chemical Co.

Diethylene Glycol [111-46-6] is obtained from the Sigma Aldrich ChemicalCo.

Voranol 370 is a mixture of sucrose and glycerol propoxylated to a NW of˜800. It has an average functionality of 6.85, and is obtained from TheDow Chemical Co.

Potassium Carbonate [584-08-7] is obtained from the Sigma AldrichChemical Co.

Ethylene Diamine [107-15-3] is obtained from the Sigma Aldrich ChemicalCo.

Vanox 945 is an antioxidant package available from RT Vanderbilt Co.Inc. It is a mixture of 60-70 percent benzeneamine, —N-phenyl-, reactionproduct with 2,4,4-trimethylpentene and 2-methylpropene [184378-08-3],20-25 percenttetrakis(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate))methane[6683-19-8], 9 percent petroleum process oil, <3.0 percent DMSextractable material [64742-52-5], <1 percent diphenylamine [122-39-4],1 percent phenothiazine [92-84-2].

Irganox 5057 is benzeneamine, —N-phenyl-, reaction product with2,4,4-trimethylpentene [68411-46-1] available from Ciba Co.

Tin (II) Octanoate [301-10-03 is available from City Chemical Co.

Ti (IV) isopropoxide [546-68-9] is obtained from the Sigma AldrichChemical Co.

Stannous Octanoate [301-10-0] is available from City Chemical Co.

Calcium acetate (62-54-4] is obtained from Sigma Aldrich Chemical Co.

Tin (II) ethyl hexanoate [301-10-0] is obtained from Sigma AldrichChemical Co.

Dibutyltin dilaurate [77-58-7] is available from Sigma Aldrich ChemicalCompany of Milwaukee, Wis.

Lipase catalyst is derived from candida antarctica and is supported onacrylate beads. This polymer-supported lipase catalyst is available fromSigma Aldrich Chemical Company of Milwaukee, Wis.

Hydroxyl equivalent weight analysis is performed by the Olin Titrationmethod.

Percent acidity is measured by the ASTM test method designation D4662-93.

Molecular weight values (Mn, Mw, Mz, Mp, PD) are measured by gelpermeation chromatography using Polymer Labs PL Gel columns andpolyethylene oxide or polystyrene standards.

Examples 1-17 A General Polymerization Procedure for Seed Oil PolyolsProduced from Fatty Acid Methyl Esters

Hydroxymethylated fatty acid methyl ester monomer was transferred into athree-necked reaction flask between 500 ml and 5000 ml in capacity, thechoice of which is commonly known to those skilled in the art and isdependent on the amount of starting materials used. The reactor wasequipped with a mechanical stirrer, packed condenser, nitrogen purge,heating mantle with thermowatch and a thermometer. A vacuum lineequipped with a dry ice trap and vacuum regulator was attached.Initiator and monomer were added and the contents of the reactor stirredand degassed while heating to 50 degrees under 20 torr vacuum. Once thetemperature was stable, catalyst was added and the temperature wasincreased to the final specified reaction temperature. The initialsetting for the vacuum was started at 100 torr and the pressure wasdecreased slowly to 5-20 torr. Heating was continued at the specifiedreaction temperature until methanol-loss was no longer visible, usuallyat least about 1 hour, and no more than 28 hours. Heating was continuedand a slow flow of nitrogen was added through the nitrogen purge whilestill maintaining a pressure of 5 to 20 torr. Polymerization was allowedto continue for at least 1 hour and no more than 28 hours. In somespecified cases an antioxidant such as Vanox 945 or Irganox 5057 wasadded just before the fluid polymer is transferred to a glass jar undernitrogen.

The following tables describe the recipes used to produce polyols of theinvention. The following examples of the invention are meant toillustrate but not limit the scope of the invention. In all tables, theterm “M/I ratio” is meant to indicate the molar ratio ofhydroxymethylated fatty acid methyl ester monomer to the initiator. Thecatalysts are identified according to the following designations: Sn(II)is stannous octanoate; Sn(IV) is dibutyl tin dilaurate; Ti(IV) istitanium tetraisopropoxide; Ca is calcium acetate.

Examples 1-10 Polyols Produced from 9(10)-Hydroxymethyl Stearate

Polyols were produced from 9,(10)-hydroxymethyl stearate using thespecified initiator and catalyst using the above procedure and asdetailed in the below Table I. TABLE I Examples 1-10 Polyol Propertiesand Run Conditions: Vis- M/I Temp Run cosity Example Initiator Initiatormole Catalyst (deg Time (cP at Acidity Hydroxyl # (moles) Name ratio(PPM) C.) (hr) 25 C.) (meq/g) percent HEW Mp Mn Mw Mz PD 1 0.483Glycerol 8.38 Sn(II) 205 27  260 0.0145 4.209 404 430 786 1210 1841 1.53996 2 0.2463 Trimethylol 1.5 Sn(II) 210 14 — — 1.49 1140 7863 412510,222 19,111 2.48 propane 97 3 0.0337 1,4-Hexanediol 9.04 Sn(II) 210 14— — 1.62 1047 8617 5088 13,217 25293 2.60 2400 4 0.757 CEI-1200 4.68Sn(II) 205 4 3410 0.0112 2.088 814 4200 2937 4427 6192 1.51 1000 5 0.422CEI-625 6.99 Sn(II) 195 12 6100 0.0064 2.3674 718 5281 2847 4823 70351.69 1227 6 0.6223 CEI-625 6.51 Sn(II) 205 24 2920 0.00168 1.999 8505440 3118 5295 7473 1.6982 1012 7 0.6243 CEI-625 6.48 Ti(IV) 205 3 45400.0030 2.123 801 4451 2893 4524 6340 1.56 1018 8 0.6234 CEI-625 6.54Sn(IV) 205 1 2420 0.0023 1.837 925 3803 2629 3591 4573 1.37 995 9 0.4049CEI-625 10.0 Ca 205 27 3170 0.00392 1.746 974 5073 2967 5248 7552 1.772494 10 0.060 Tetrol 800 5.09 Ti(IV) 205 14 2790 — 2.56 663 5678 30736189 11,675 2.01 1000

Examples 11-18 Polyols Produced from Hydroxymethylated Fatty Acid MethylEsters of Vegetable Oils

The vegetable oil based polyols were produced using the above generalprocedure from the hydroxymethylated fatty acid methyl esters of soybeanoil and these polyols are shown in the below Table II. TABLE II Example11-18 Properties and Reaction Conditions: Run Initiator Initiator M/ICatalyst Temp Time Viscosity Acidity Hydroxyl Example # (moles) Namemole ratio (PPM) (deg C.) (hr) (cP at 25 C.) (meq/g) percent HEW Mp MnMw Mz PD 11 0.395 CEI-625 7.96 Sn(II) 195 12 5140 0.0030 2.02 841 44722959 5018 6770 1.70 1188 12 0.523 CEI-625 5.98 Sn(II) 195 12 41000.00248 2.254 754 4009 2615 4342 6413 1.66 1365 13 0.512 CEI-625 5.95Sn(II) 195 6 2730 0.00064 1.881 904 3118 2347 3612 5185 1.54 891 140.404 Tetrol 600 9.98 Sn(II) 205 3 2680 0.0086 1.512 1124 4643 2877 45956410 1.60 995 15 1.445 CEI-625 6.03 Sn(II) 195 10 3450 0.00143 2.2524755 3977 2858 4304 6065 1.51 701 16 0.637 CEI-625 5.99 Sn(II) 195 123720 0.0059 2.233 761 4000 2687 4270 6152 1.59 827 17 2.09 PE-270 1.0Sn(II) 195 9 4100 0.0037 11.67 145 1082 1053 1450 2014 1.38 1097 18 1.25CEI-625 1.55 Sn(II) 195 10 1160 0.00401 5.22 325 1299 1491 2047 28611.37 1034

Examples 19-22 Large Scale Preparation of Vegetable Oil Based PolyolsUsing CEI-625 Initiator and Stannous Octanoate Catalyst

Hydroxymethylated methyl esters of soybean oil and CEI-625 were combinedin a reactor with stirring, and the oxygen was purged from the reactorby pulling a vacuum on the reactor and refilling the reactor withnitrogen. Catalyst (stannous octanoate) was added to the reactor andagitation was continued. A slow nitrogen sparge was fed to the reactorand the mixture was heated to 205° C. while maintaining a vacuum of 80torr. The heating was continued for a minimum of 4 hours under aconstant vacuum with a slow nitrogen sweep. The mixture was cooled to62° C. and the antioxidant Irganox 5057 (121 grams) was added withcontinuing agitation.

In the following examples, FAME indicates the source of the fatty acidmethyl ester used for the polymerization, with HMS indicatinghydroxymethyl stearate and Soy indicating hydroxymethylated soybean oil.The catalyst Sn(II) is stannous octanoate. The properties and reactionconditions of the polyols of Examples 19-22 are shown in Table III.TABLE III Properties and Reaction Conditions of Examples 19-22 InitiatorM/I Run Viscosity FAME CEI-625 mole Catalyst Temp Time (cP at AcidityHydroxyl Example # Kg Kg ratio PPM (deg C.) (hr) 25 C.) (meq/g) percentHEW Mp Mn Mw Mz PD 19 HMS 11.39 10:1 Sn(II) 225 4.5 2800 0.00354 2.06825 5136 3121 5136 7179 1.6456 38.83 1002 20 HMS 20.59 10:1 Sn(II) 205 43010 0.000713 2.0421 832 4970 3015 5039 7072 1.6713 70.31 1000 21 Soy11.8  6:1 Sn(II) 195/20 12 3940 0.002 2.256 772.30 4040 2669 4367 64031.64 26.15 1005 22 Soy 11.8  6:1 Sn(II) 195/20 12 3570 0.00489 2.363779.56 3925 2578 4293 6409 1.67 26.15 1000

Examples 23-24 Lipase-Catalyzed, Saccharide-Initiated Polyols

Hydroxymethylated fatty acid methyl ester monomer prepared from soybeanoil was transferred into a three-necked reaction flask between 1000 mland 5000 ml in capacity, the choice of which is commonly known to thoseskilled in the art and is dependent on the amount of starting materialsused. The reactor was equipped with a mechanical stirrer, packedcondenser, nitrogen purge, heating mantle with thermowatch and athermometer. A vacuum line equipped with a dry ice trap and vacuumregulator was attached.

The reactants (monomer and initiator) were weighed into the flask andheated to 50° C. under 20 torr vacuum. Following this degassing step,the catalyst (0.5 g) was added. The reactor was maintained at 50° C. at20 torr vacuum for 6 hours. Then the reactor was heated to 60° C. under20 torr vacuum and held there for 12 more hours. The reactor was cooledto 50° C. and the product filtered through a funnel with a plug of glasswool. The product solidified on standing at room temperature and thispolyol's properties and reaction conditions are shown in Table IV. TABLEIV Properties and Reaction Conditions of Examples 23 and 24. Lipase RunInitiator Initiator M/I Catalyst Temp Time Viscosity Acidity HydroxylExample # (moles) Name Mole ratio (g) (deg C.) (hr) (cP at 25 C.)(meq/g) percent HEW Mp Mn Mw Mz PD 23 0.0786/ Glycerol/ 1.49 0.50 50 425300 0.0356 8.110 209.6 836 1126 1454 2542 1.29 0.0672 Sucrose 24 0.0798Glycerol 8.34 0.50 50 42 592 0.00643 3.563 477.1 800 1207 1504 1954 1.25

Examples 25-26 Saccharide-Initiated Seed Oil Polyols Produced with NMPCosolvent

Hydroxymethylated fatty acid methyl ester monomer derived from soybeanoil was transferred into a three-necked reaction flask between 1000 mland 5000 ml in capacity. The reactor was equipped with a mechanicalstirrer, packed condenser, nitrogen purge, heating mantle withthermowatch and a thermometer. A vacuum line equipped with a dry icetrap and vacuum regulator was attached. The reactants (monomer andinitiator) were weighed into the flask and heated to 195° C. under 20torr vacuum. The system was maintained at this temperature for 3 hoursduring which time water was removed from the system. The system washeated to 195° C. under 20 torr vacuum for 5 hours to remove theremainder of the water.

The system was opened and 0.71 gram of catalyst was added. The reactorwas heated to 195° C. under 20 torr vacuum and held there for 6 hours.The reactor was cooled to 170° C. and 522 grams of NMP and another 0.71gram catalyst charge was added. The temperature was maintained for 2hours. Then 40 g of potassium carbonate was added and the vacuum wasmaintained at 100 torr. The temperature was maintained for 3 hours. Thereactor contained a clear dark amber very viscous liquid. The NMP wasremoved. After no more NMP could be removed the reactor was shutdown andleft at 80° C. to avoid solid formation. The reactor was heated to 180°C. and slowly dumped through a funnel containing a plug of glass wool toremove any solid carbonate. A heat lamp was necessary to keep the liquidflowing. In these Examples, the catalysts Sn(II) was stannous octanoate.The properties and run conditions for Examples 25 and 26 are shown inTable V. TABLE V Properties and Run Conditions of Examples 25 and 26.M/I Catalyst Run Initiator Initiator Mole (PPM) Temp Time ViscosityAcidity Hydroxyl Example # (moles) Name ratio Sn(II) (deg C.) (hr) (cPat 25 C.) (meq/g) percent HEW Mp Mn Mw Mz PD 25 0.98 Sorbitol 3.0 1204195 8 >196000 0.01007 7.064 240 5856 2750 4885 7433 1.78 26 1.90Pentaerythritol 2.0 942 205 10 >196000 0.00335 6.223 273 1213 2904 45426670 1.56

Examples 27-28 Seed Oil Polyols Produced with Sn(II)/K₂CO₃ Cocatalysts

In the following examples the catalysts are identified according to thefollowing designations: Sn(II) is stannous octanoate, and K₂CO₃ ispotassium carbonate.

Hydroxymethylated fatty acid methyl ester monomer was transferred into athree-necked reaction flask between 1000 ml and 5000 ml in capacity, thechoice of which is commonly known to those skilled in the art and isdependent on the amount of starting materials used. The reactor wasequipped with a mechanical stirrer, packed condenser, nitrogen purge,heating mantle with thermowatch and a thermometer. A vacuum lineequipped with a dry ice trap and vacuum regulator was attached.

The reactants (monomer and initiator) were weighed into the flask andheated to 90° C. under 100 torr vacuum. After 30 minutes, the vacuum wasbroken and K₂CO₃ was added. The reactor was heated to 120° C. under 100torr vacuum, and after 1 hour the stannous octanoate was added. Thepressure was decreased to 50 torr and the system became visibly viscousand slightly yellow after 6 hours. The reactor was heated to 60° C. andthe product was transferred to a storage container. TABLE VI Propertiesand Conditions of Examples 27 and 28. K2CO3/ M/I Sn(II) Run InitiatorInitiator Mole Catalyst Temp Time Viscosity Acidity Hydroxyl Example #(moles) Name ratio (PPM) (deg C.) (hr) (cP at 25 C.) (meq/g) percent HEWMp Mn Mw Mz PD 27 1.14 Voranol 0.90 4699/509 90-110 6 2680 0.00081 9.338182 831 795 826 858 1.04 370 28 1.02 Diethylene 2.93 7040/598 120 6 3230— 4.075 417 3573 2823 4064 5657 1.44 Glycol

Example 29 Seed Oil Polyol Produced from Amine-Containing Initiator

The hydroxymethylated fatty acid methyl ester mixture derived fromsoybean oil (soy monomer) (100 g) was transferred into a 250-mlthree-neck flask equipped with a magnetic stirrer, condenser/nitrogenpurge with moisture trap, a heating mantle with thermowatch and athermometer. Ethylenediamine (9.12 g) was added and heated to 140° C.under N₂. Once the temperature was stable, Tin (II) 2-ethylhexanoatecatalyst (0.1133 g) was added and the mixture was stirred overnight. Thenitrogen line was then replaced with a vacuum line. Vacuum was graduallydrawn down to 50 torr. The reaction was monitored periodically to insurethe vacuum was stable. The polymerization was continued overnight. Thevacuum was removed and the polyol was cooled and collected. The polyolat 25° C. was a solid and the Mp, Mn, Mw, Mz and PD of the polyol was955, 1034, 1316, 1598 and 1.27.

Example #30 Seed Oil Polyol Produced with a Different Order of Additionof the Monomer and Initiator

The VOB monomer (the hydroxymethylated fatty acid methyl ester mixturederived from soybean oil) only was weighed (8.5 moles) into the flaskand the reactor was heated under 20 torr vacuum to 50° C. Following thedegassing the vacuum was broken and 1.58 g of catalyst (tin IIOctonoate) was added and the system heated to 195° C. at 20 torr. Thereaction was closely monitored to make sure that the homopolymerizationwas not allowed to go so far as to gel. After 4 hours, the solution wasnoticeably viscous even at 195° C., the reactor was shutdown, sampled,and left under nitrogen overnight. CEI-625 initiator was weighed (1.38moles) into the flask and the reactor heated to 195° C. under 20 torrvacuum. The solution was noticeably turbid even after heating. Afterabout 2 hours at 195° C., the system had cleared and the solution wasmuch less viscous. After about 8 hours the reactor was cooled to 100° C.and 9.1 grams of Irganox 1076 and 5.1 grams of Vanox 945 were added andthe polyol was collected into a glass storage container. The propertiesof this polyol appear in Table VII. TABLE VII Properties of Example 30Viscosity Acidity Hydroxyl Example # (cP at 25 C.) (meq/g) percent HEWMp Mn Mw Mz PD 30 3440 0.00323 2.573 660 4725 3163 4560 6184 1.44

Examples 31-67 Methods for Production of Polyurethanes from Seed OilPolyols

All foam samples are prepared in a consistent manner according to thefollowing general procedure.

Chemical components which are used for the preparation of flexible andrigid polyurethane foams include but are not limited to:

Diethanolamine (DEOA) is a molded foam crosslinker which is availablefrom The Dow Chemical Co.

Dabco 33LV is a 33 percent crystalline diethylenetriamine in 67 percentdipropylene glycol. It is a molded foam catalyst which is available fromAir Products and Chemicals, Inc.

Dabco DC 5164 is a molded foam silicone surfactant which is availablefrom Air Products and Chemicals, Inc.

Tegostab-b8708 a molded foam silicone surfactant which is available fromDegussa Goldschmidt Chemicals Corp.

Niax A-400 is a molded foam amine catalyst consisting of 40 percenttertiary amine/carboxylic salt (trade secret), 40 percent water, 20percent bis(2-dimethylaminoethy)ether, and 4 percent hydroxyl compound(trade secret). Available from Crompton OSi Specialties Co.

Niax A-300 is a molded foam amine catalyst consisting of 40 percenttertiary amine/carboxylic salt (tradesecret), 20 percenttriethylenediamine, and 40 percent water, available from Crompton OSiSpecialties Co.

Polycat 58 is a proprietary composition amine catalyst used in moldedfoams, available from Air Products and Chemicals.

Polycat 5 is pentamethyl diethylene triamine. A rigid foam catalystwhich is available from Air Products and Chemicals, Inc.

Polycat 8 is N,N-dimethyl cyclohexylamine. A rigid foam catalyst whichis available from Air Products and Chemicals, Inc.

DC-5160, a flexible slabstock foam silicone surfactant is available fromAir Products & Chemicals, Inc.

L-626 is a low-resiliency viscoelastic flexible slabstock foamsurfactant available from Crompton Corp.

D-8264, is an optimized amine catalyst blend for slabstock foamavailable from Air Products & Chemicals, Inc.

Water used for these formulations is distilled, deionized water.

T-95, which is stannous octanoate catalyst, 33 percent by weight indioctylphthalate is available from Air Products and Chemicals, Inc.

Voranol 3137A, which is a 2.7 average functional, 13 wt. percentethylene oxide, heterofed 3100 MW polyol which is available from The DowChemical Company.

Voranol 3943A, which is an 1807 equivalent weight copolymer polyol basedon Voranol 3136 (A 3100 MW 13 percent EO hetero clear polyol) and 43 wt.percent styrene/acrylonitrile solids, is available from The Dow ChemicalCompany.

Voranol 3512: A 2.7 functional, 3500 MW 13 percent wt. percent ethyleneoxide, heterofed polyol, is available from The Dow Chemical Company.

Voranol 3010, which is a 2.8 functional, 3000 MW 8 percent ethyleneoxide heterofed polyol, is available from The Dow Chemical Company.

Voranol 3022J, which is a 2.6 functional, 3000 MW all propylene oxidepolyol, is available from The Dow Chemical Company.

Specflex NC-632 is a 4.7 functional, propylene oxide block plus 15percent ethylene oxide capped 1750 EW polyol used in flexible moldedfoam. Available from The Dow Chemical Co.

Specflex NC-700 is a 40 percent solids (styrene-acrylonitrile) copolymerpolyol based on Voranol 4735 (a 3.0 functional, propylene block plus 17percent ethylene oxide capped polyol with a 1580 equivalent weight) usedin flexible molded foams. Nominal equivalent weight is 2600. Availablefrom The Dow Chemical Co.

Voranol 3136: A 2.7 average functionality, 13 wt. percent ethylene oxideheterofed 3100 MW polyol used to make slabstock foam. Available from TheDow Chemical Co.

Voranol CP 1421: A 2.94 average functionality, 80 percent ethylene oxideheterofed 5000 MW polyol used in flexible slab and molded foams which isavailable from The Dow Chemical Co.

DABCO T-9 is stabilized stannous octanoate, a catalyst used in flexibleslabstock foams, available from Air Products and Chemicals, Inc.

VORANATE T-80 is type I TDI (toluene diisocyanate) with an equivalentweight of 87. Used in making flexible foams, it is available from TheDow Chemical Co.

PAPI 27 is a 2.7 functional polymeric MDI (methylenediisocyanate) withan equivalent weight of 134. Used in making rigid foams and availablefrom The Dow Chemical Co.

Firemaster-550 is a mixture of halogenated aryl esters and aromaticphoshates. Used as a flame retardant in flexible foams. Available fromGreat Lakes Chemical Co.

L6900 is a silicone surfactant used in rigid foams. Available fromCrompton Osi Specialties Co.

HCFC Forane 141b is a hydrochloroflourocarbon blowing agent used inrigid foams. Available from Atonfina Chemicals, Inc.

Dypol 6862 is a solvent free pale yellow branched poly alcohol withester and ether groups, available from Dyflex.

Baylith L is a 50 percent mixture of 3 angstrom molecular sieves inCastor oil, available from Bayer.

VORANATE M 220 is a polymeric MDI functionality 2.7 available from TheDow Chemical Company.

ISONATE M 143 is a carbodiimide modified pure MDI available from The DowChemical Company.

General Procedure for the Production of Polyurethanes from VegetableOil-Based (VOB) Polyols

All of the polyol components of a given formulation except the tincatalyst (stannous octanoate in dioctylphthalate, T-95), wereindividually metered and weighed into a one quart capacity metal cup.The contents were premixed for 15 seconds at 1800 rpm using a pin typemixer. The tin catalyst, dispensed by volume, was then added to thestirred components and mixed for an additional 15 seconds at 1800 rpm. Astoichiometric amount of Toluene Diisocyanate (Voranate T-80), was thenadded to the cup and vigorously mixed for 3 seconds at 2400 rpm. The cupcontents were then poured into a 15″×15″×10″ wooden box lined with apolyethylene bag. The blowoff time and any other distinct reactioncharacteristics were recorded. The foam buns were allowed to cureovernight under a ventilated fume hood. They were then placed in ambientstorage and submitted for physical property assessment using ASTM testmethod designation D 3574-95.

Where indicated, other slabstock foam data were generated onconventional continuous machines (Polymech or UBT) featuring areciprocating mixing head and high pressure injection of all streamsexcept the polyol. The polyol and isocyanate temperatures weremaintained at around 23° C. The polyol output was 20 kg/min. (Thepolyols used in Examples 34-36 and Examples 49-51 were blended withVoranol 3137A either in the polyol tank or in the mixing head.).

According to the general procedure, the foams were prepared according tothe following formulations, with the results of mechanical testingincluded in the tables: TABLE VIII Examples 31-33. Box foams preparedfrom hydroxymethyl stearate polyols Example # 31 32 33 ComponentsV-3137A 80 65 50 Polyol of Example # 6 20 35 50 Water 4.5 4.5 4.5 D-82640.12 0.12 0.12 DC5160 1 1 1 T-95, mils 0.4 0.4 0.4 Index 110 110 110 TDI57.8 58.2 58.5 Properties Blow-Off 96 95 94 Air Flow 4.2 4.3 3.3 Com.Set. 3.7 4.3 4.4 Density 1.44 1.54 1.51 25 percent IFD 39.8 41.3 43.2 65percent IFD 71.6 76.8 82.1 Guide Factor 27.6 26.8 28.6 Resiliency 38 3736 Tensile 12.7 12.5 12.1 Tear 1.7 1.7 1.6 Elongation 104 90 74

TABLE IX Examples 34-36. Flexible slabstock foam produced fromhydroxymethyl stearate polyols on a continuous foam machine: Example #34 35 36 Components Voranol* 3137A 80 65 50 Combined Polyols of Examples# 19 20 35 50 and #20 Water 4.5 4.5 4.5 D-8264 0.12 0.12 0.12 DC-51601.0 1.0 1.0 DABCO T9 0.2 0.2 0.2 Voranate T-80 57.8 58.1 58.4 FoamProperties Density (kg/m3) 21.1 21.2 21.4 CFD 40 percent (kPa) 3.9 4.34.5 IFD 40 percent 156.2 168.4 175.9 SAG Factor 2.7 2.8 2.9 Hysterisis(percent) 45 49 53 Resilience (percent) 40 36 36 Guide Factor 7.4 7.98.2 Airflow (cfm) 3.1 2.4 2.1 Tensile (kPa) 89 80 78 Elongation(percent) 142 128 102 Tear (N/m) 426 337 309These Examples were produced on a continuous slabstock foam productionmachine at a TDI index of 110.

TABLE X Examples 37-41. Flexible molded foam produced from hydroxymethylstearate polyols Example # 37 38 39 40 41 Components Specflex NC-63270.00 60.00 50.00 70.00 70.00 Specflex NC-700 20.00 20.00 20.00 20.0020.00 Combined Polyols of Examples 10.00 20.00 30.00 10.00 10.00 #19 and#20 Voranol* CP 1421 1.00 Polycat 58 0.30 Niax A-300 0.25 0.25 0.25 0.250.25 Niax A-400 0.10 0.10 0.10 0.10 0.10 Tegostab-b8708 0.80 0.80 0.800.80 0.80 Dabco 33LV 0.30 0.30 0.30 0.30 0.30 Dabco DC 5164 0.20 0.200.20 0.20 0.20 DEOA PURE 1.00 1.00 1.00 1.00 1.00 WATER 3.70 3.70 3.703.70 3.70 TOTAL PARTS 106.35 106.35 106.35 107.35 106.65 WATER CONTENTOF THE BLEND 3.65 3.65 3.65 3.61 3.64 OH# OF THE POLYOL BLEND 56.9160.24 63.58 56.60 59.72 INDEX 100 100 100 100 100 Foam PropertiesDensity Core 32.1 32.8 33.2 33.5 33.0 CFD 50 percent 4.9 5.5 5.6 5.0 4.7Tensile Strength 106 114 125 109 102 Elongation 104 101 106 105 100 TearStrength 281 271 284 255 266 Resilience 58 57 55 57 61 Air Flow 1.612.49 1.68 2.28 2.62 Compression Set 50 6.5 6.4 8.1 6.0 6.2 percentCompression Set 90 11.3 11.3 13.5 8.7 9.7 percent Wet Compression set 7021.3 20.7 24.3 17.0 22.1 percent

TABLE XI Examples 42-44. Flexible foam produced from seed oil polyol asa 35 percent and 50 percent (w/w) blend with conventional EO/PO polyol.Example # 42 43 44 Components V-3137a 65 50 65 Polyol of Example # 12 3550 Polyol of Example # 13 35 Water 4.5 4.5 4.5 DC-5160 1 1 1 D-8264 0.120.12 0.12 T-95 0.4 0.5 0.7 Index 110 110 110 TDI 58.4 58.9 57.7 Blowoff126 105 95 Airflow (cfm) 4.3 2.5 2.6 Density (pcf) 1.48 1.41 1.4 Tear(pli) 1.4 1 1.3 Mean(psi) 12.2 13.3 12.8 percent Elongation 69.5 67.883.7 CS_90orig 4.2 4.9 4.3 IFD_Slab: 25 percent lbs. 39.2 47.2 44.9 65percent lbs. 76.3 92.2 84.3 Resilency 30 33 33 GuideFactor 26.5 33.532.1

TABLE XII Example 45: Flexible foam produced from seed oil polyol as a65 percent (w/w) blend with conventional EO/PO polyol Example # 45V-3136 35 Polyol of Example #15 65 Water 4.5 D-8264 0.12 L-626 1 DC51601 T-95, mils 0.32 Index 110 TDI 59.4 Blow-Off (sec) 88 Air Flow Notdetermined Com. Set. Not determined Density Not determined 25 percentIFD Not determined 65 percent IFD Not determined Guide Factor Notdetermined Resiliency Not determined Tensile Not determined Tear Notdetermined

TABLE XIII Examples 46-48: Flexible foams produced from seed oil polyolas 100 percent of the polyol component, and at different isocyanateindices Example # 46 47 48 V-3137A Polyol of 100 100 100 Example # 15Water 4.5 4.5 4.5 D-8264 0.12 0.12 0.12 L-626 3 3 3 DC5160 T-95, mils0.38 0.28 0.38 Index 100 110 120 TD 57.4 63.1 68.8 Blow-Off 87 104 AirFlow 0.91 0.63 0.31 Density 1.56 1.52 1.48 25 percent 39.6 37.8 49.6 IFD65 percent 87.9 93.6 95.5 IFD Guide 25.4 24.9 33.5 Factor Resiliency 2829 32

TABLE XIV Examples 49-51: Continuous Production of flexible slabstockfoam from vegetable oil based polyol at 20 percent, 35 percent and 50percent Example # 49 50 51 Components V-3137 80 65 50 Combined Polyol of20 35 50 Examples # 21 and #22 Water 4.5 4.5 4.5 D-8264 0.12 0.12 0.12DC5160 1 1 1 DABCO T-9 0.16 0.14 0.12 Index 110 110 110 Voranate T8057.4 58.4 58.8 Properties Air Flow 4.5 4.1 4.1 Compression Set 75 3.54.7 7.8 percent Density (kg/m{circumflex over ( )}3) 22.8 23.4 22.5 40percent IFD 166.6 167.5 186.4 Guide Factor 7.3 7.2 8.3 SAG 2.7 2.7 2.9Resiliency (percent) 42 39 39 Tensile (kPa) 60 61 75 Tear (N/m) 279 266194 Elongation 88 93 71

TABLE XV Example 52: Flexible foam produced from seed oil polyol withcopolymer polyol Example # 52 Components Voranol-3136 15 Voranol-3943A35 Polyol of Example 50 # 15 Water D-8264 0.12 DC5160 1 T-95, mils 0.32Index 110 TDI 57.5 Blow-Off (sec) 93 Air Flow 4 Com. Set. 1.9 Density1.48 25 percent IFD 37.61 65 percent IFD 92.3 Guide Factor 25.4Resiliency 31

TABLE XVI Examples 53-56: Flexible molded foams produced from seed oilpolyol with copolymer polyol: Example # Components 53 54 55 56 SpecflexNC-632 70.00 60.00 50.00 40.00 Specflex NC-700 20.00 20.00 20.00 20.00Combined Polyols from 10.00 20.00 30.00 40.00 Examples #21 and #22Voranol CP 1421 Polycat 58 Niax A-300 0.25 0.25 0.25 0.25 Niax A-4000.10 0.10 0.10 0.10 Tegostab-b8708 0.80 0.80 0.80 0.80 Dabco 33LV 0.300.30 0.30 0.30 Dabco DC 5164 0.20 0.20 0.20 0.20 DEOA PURE 1.00 1.001.00 1.00 WATER 3.70 3.70 3.70 3.70 TOTAL PARTS 106.35 106.35 106.35106.35 WATER CONTENT OF 3.65 3.65 3.65 3.65 THE BLEND OH# OF THE POLYOLBLEND 57.71 61.84 65.98 70.12 INDEX 100 100 100 100 Density Core 35.436.8 35.5 33.8 CFD 50 percent 5.6 6.6 6.2 6.4 Tensile Strength 107 134109 107 Elongation 103 107 93 84 Tear Strength 223 220 237 198Resilience 53.5 52 48.5 43.5 Air Flow 1.0 1.7 1.5 1.3 Hardness Lossafter Fatigue 32 34 37 40 Compression Set 50 percent 7 8 10 12Compression Set 90 percent 9 10 14 17 Wet Compression set 70 percent 1720 22 24

Example 57 Flexible Foam Produced from Seed Oil Polyol Using High WaterLevel in the Formulation

TABLE XVII Example 57 Components and Characteristics. Example # 57V-3137A 50 Polyol of 50 Example #16 Water 6 D-8264 0.1 DC5160 1 T-95,mils 0.35 Index 110 TDI 75.1 Blow-Off 107 Air Flow 4.3 Density 1.15 25percent 33.5 IFD 65 percent 78.8 IFD Guide 29.1 Factor Resiliency 34

Examples 58-62 Rigid Foams Prepared from Seed Oil Polyols GeneralProcedure for the Production of Rigid Foams

Foam components were measured to an appropriate total blended mass whichwas appropriate for the size of the container into which the foam willbe formed, according to the ratios in the Table XVIII for Examples58-62. The isocyanate component was weighed into a mixing cupseparately. All components except for the isocyanate were combined in amixing cup and stirred at 1000 rpm for 6 seconds. The isocyanate wasthen added to the blend of all other components in the polyol, and thisnew mixture was blended at 1000 rpm for 6 seconds. The foam mixture wasthen poured into the container in which the foam was to be formed. Thefollowing characteristics were measured: gel-time which is defined aswhen a tongue depressor inserted into the foam draws strings whenremoved (not surface stringing but stringing from foam Interior), andtack free-time which is defined as when the foam surface is no longertacky, or does not adhere to touch. Results of these Examples are shownin Table XVIII TABLE XVIII Results of Examples 58-62 Example # 58 59 6061 62 Components Voranol 360 50 75 50 25 0 Polyol of Example #25 50Polyol of Example #27 25 50 75 100 Polycat 5 1 1 1 1 1 Polycat 8 2 2 2 22 Polycat 46 1 1 1 1 1 L-6900 2.15 2.15 2.15 2.15 2.15 Water 2.58 2.582.58 2.58 2.58 HCFC-141b 20 20 20 20 20 PAPI 27 137 137 137 137 137Properties Gel Time (sec) 29 35 41 40 30 Tack Free (sec) 40 63 66 65 45Crown Density (lbs/cft) 1.59 1.41 1.38 1.499 1.446

Examples 63 and 64 Elastomers and Coatings Prepared from VegetableOil-Based Polyol

Polyols of the examples were blended together by adding molecular sieves(Baylith L) and mixing by hand for 5 minutes. The blend is then degassedin a vacuum oven until no bubbles were retained.

Method for Production of an Elastomer Plate or a Coating

The polyol of the example and the isocyanate were mixed at roomtemperature for a minimum of 1 minute to achieve complete homogeneity.The resulting mixture was cast into a mold of 2 mm thickness forpreparation of an elastomer, or cast onto a flat surface for thepreparation of a coating. Curing of a thin layer (2 mm) at atmosphericcondition gave a good elastomer without bubbles. Alternatively, thecasting was cured in an oven for 1 hour at 75° C.

The resulting polyurethane sample was kept at room temperature for 7days before testing, or alternatively was post cured at 75° C. 10 hoursbefore testing. TABLE XIX Examples 62 and 63 Components and Results.Example # 62 63 Components Castor oil Dypol 6862 Polyol of Example #18100 100 Baylith L 5 5 VORANATE M 220 42.5 ISONATE M 143 45.5 PropertiesTensile strength MPa 4.7 4.0 Elongation percent 56 76 Tear strength N/cm56 56 Pot life (geltimer) min 48 55 Shore A (7days) 70 73 Shore D (7days) 24 20

1. A vegetable oil based polyol comprised of

where R is a residue of a polyol, polyamine or aminoalcohol initiator; Xand X′ may be the same or different and is O, N or NH; p is an integerfrom 1 to 5; q is an integer from 1 to 5 wherein p+q is from 3 to 8, tis an integer from 3 to 8 and A may be the same or different and isselected from the group consisting of A1, A2 and A3 where

where m, n, v, r, s, a, b and c are integers and m is greater than 3, ngreater than or equal to zero and m+n is from 11 to 19, v is greaterthan 3, r is greater than or equal to zero, s is greater than or equalto zero and v+r+s is from 10 to 18, a is from 0 to 35, b is from 0 to 35and c is from 0 to 35, so long as that all a's, b's and c's in anymolecule of the vegetable oil based polyol are not all zero and(a+b+c)/(p+q+t) is about 5 to about 100 in the vegetable oil basedpolyol.
 2. The vegetable oil based polyol of claim 1 wherein at least aportion of A is A3.
 3. The vegetable oil based polyol of claim 2 whereinthe amount of A3 present in the vegetable oil based polyol is at leastabout 0.01 percent to 25 percent by weight of the vegetable oil basedpolyol.
 4. The vegetable oil based polyol of claim 1 wherein theinitiator is of a polyol, polyamine or aminoalcohol that has a primaryhydroxyl or primary amine and a secondary hydroxyl or secondary aminegroup.
 5. The vegetable oil based polyol of claim 4 wherein theinitiator has a secondary hydroxyl group.
 6. The vegetable oil basedpolyol of claim 4 wherein at least a portion of the vegetable oil basedpolyol has a structure

where at least one X′—H group is a primary hydroxyl or primary amine andat least one X-A-H is located at a position corresponding to a secondaryhydroxyl or secondary amine of the initiator.
 7. The vegetable oil basedpolyol of claim 6 wherein at least a portion of the vegetable oil basedpolyol has a structure:

where all of the X′—H groups are a primary hydroxyl or primary amine andall of the X-A-H groups are located at a position corresponding to asecondary hydroxyl or secondary amine of initiator.
 8. The vegetable oilbased polyol of claim 7 wherein the initiator is selected from the groupconsisting of trimethylolpropane; pentaerythritol; sorbitol; sucrose;glycerol; bis-3-aminopropyl methylamine; diethylene triamine;9(1)-hydroxymethyloctadecanol, 1,2,6-hexanetriol; any of theaforementioned where at least one of the alcohol or amine groups presenttherein has been reacted with ethylene oxide, propylene oxide or mixturethereof; and combination thereof.
 9. The vegetable oil based polyol ofclaim 1 wherein the initiator is glycerol, pentaerythritol, sucrose,sorbitol, an ethoxylated glycerol, propyxylated glycerol, ethoxylatedpentaerthritol, propyxylated glycerol or mixture thereof.
 10. Thevegetable oil based polyol of claim 1 wherein the initiator is glycerolor glycerol where at least one of the alcohol groups of the glycerol hasbeen reacted with ethylene oxide or propylene oxide.
 11. The vegetableoil based polyol of claim 10 wherein the initiator is glycerol.
 12. Avegetable oil based polyol comprised of

where R is a residue of a polyol, polyamine or aminoalcohol initiator; Xand X′ may be the same or different and is O, N or NH; p is an integerfrom 1 to 5; q is an integer from 1 to 5 wherein p+q is from 2 to 8, tis an integer from 2 to 8 and A may be the same or different and isselected from the group consisting of A1, A2 and A3 where

where m, n, v, r, s, a, b and c are integers and m is greater than 3, ngreater than or equal to zero and m+n is from 11 to 19, v is greaterthan 3, r is greater than or equal to zero, s is greater than or equalto zero and v+r+s is from 10 to 18, a is from 0 to 35, b is from 0 to 35and c is from 0 to 35, so long as that all a's, b's and c's areessentially not all zero, at least a portion of A is A3 and(a+b+c)/(p+q+t) is greater than 0 to about 100 in the vegetable oilbased polyol.
 13. The vegetable based oil of claim 12 wherein(a+b+c)/(p+q+t) is about 0.5 to
 50. 14. The vegetable based oil of claim13 wherein (a+b+c)/(p+q+t) is about 1 to
 25. 15. The vegetable based oilof claim 12 wherein the initiator has a secondary hydroxyl group. 16.The vegetable oil based polyol of claim 12 wherein at least a portion ofthe vegetable oil based polyol has a structure

where at least one X′—H group is a primary hydroxyl or primary amine andat least one X-A-H is located at a position corresponding to a secondaryhydroxyl or secondary amine of the initiator.
 17. The vegetable oilbased polyol of claim 16 wherein at least a portion of the vegetable oilbased polyol has a structure:

where all of the X′—H groups are a primary hydroxyl or primary amine andall of the X-A-H groups are located at a position corresponding to asecondary hydroxyl or secondary amine of the initiator.
 18. Thevegetable oil based polyol of claim 17 is wherein the initiator isglycerol.
 19. The vegetable oil based polyol of claim 12 wherein theinitiator is selected from the group consisting of neopentylglycol;1,4-cyclohexane diol; 2,5-hexanediol; 1,6-hexanediol; 1,2-propyleneglycol; trimethylolpropane; pentaerythritol; sorbitol; sucrose;glycerol; 1,6-hexanediol; 1,4-butanediol; ethylene glycol; diethyleneglycol; triethylene glycol; bis-3-aminopropyl methylamine; ethylenediamine; diethylene triamine; 9(1)-hydroxymethyloctadecanol;1,4-bishydroxymethylcyclohexane;8,8-bis(hydroxymethyl)tricyclo[5,2,1,0^(2,6)]decene; Dimerol alcohol;hydrogenated bisphenol; 9,9(10,10)-bishydroxymethyloctadecanol;1,2,6-hexanetriol; any of the aforementioned where at least one of thealcohol or amine groups present therein has been reacted with ethyleneoxide, propylene oxide or mixture thereof; and combination thereof. 20.The vegetable oil based polyol of claim 19 wherein the initiator isglycerol or glycerol where at least one of the alcohol groups of theglycerol has been reacted with ethylene oxide or propylene oxide. 21.The vegetable oil based polyol of claim 1 wherein vegetable based polyolis a liquid and has a weight average molecular weight of at least 350.22. The vegetable oil based polyol of claim 21 wherein the weightaverage molecular weight is at least about
 1500. 23. The vegetable oilbased polyol of claim 22 wherein the weight average molecular weight isat least about is
 1800. 24. The vegetable oil based polyol of claim 12wherein vegetable based polyol is a liquid and has an average molecularweight of at least about 350 by weight.
 25. The vegetable oil basedpolyol of claim 24 wherein the average molecular weight is at leastabout 1500 by weight.
 26. The vegetable oil based polyol of claim 25wherein the weight average molecular weight is at least about
 1800. 27.A process to make a vegetable based polyol, the process comprising, i)mixing an initiator that is a polyol, polyamine, aminoalcohol or mixturethereof, and a vegetable oil based monomer having at least one of theformulae:

where m, n, v, r, and s are integers and m is greater than 3, n greaterthan or equal to zero and m+n is from 11 to 19, v is greater than 3, ris greater than or equal to zero, s is greater than or equal to zero andv+r+s is from 10 to 18, and ii) heating the mixture to a reactiontemperature, for a reaction time, while under a vacuum and in thepresence of an amount of a catalyst sufficient to form the vegetablebased polyol.
 28. The process of claim 27 wherein the catalyst is a tincatalyst and the amount of catalyst is at least about 100 parts permillion by weight of the total mixture.
 29. The process of claim 28wherein the amount of catalyst is at least about 250 parts per million.30. The process of claim 27 wherein the catalyst is titanium catalystand the amount of catalyst is at least about 100 parts per million byweight.
 31. The process of claim 30 wherein the amount of catalyst is atleast about 500 parts per million.
 32. The process of claim 28 whereinthe catalyst is selected from the group consisting of tin (II)ethylheptanoate, tin (II) octanoate, dibutylytin (IV) dilaurate andcombination thereof.
 33. The process of claim 30 wherein the catalyst istitanium tetraisopropoxide, titanium tetraisobutoxide or combinationthereof
 34. The process of claim 27 wherein the catalyst is an enzymecatalyst.
 35. The process of claim 34 wherein the catalyst is lipase.36. The process of claim 27 wherein the catalyst is comprised of acarbonate catalyst.
 37. The process of claim 36 wherein the carbonatecatalyst is K₂CO₃, NaHCO₃ or combination thereof.
 38. The process ofclaim 27 wherein the initiator has at least one secondary hydroxyl orsecondary amino group.
 39. The process of claim 27 wherein the initiatoris glycerol.
 40. The process of claim 27, wherein the initiator hasvolatility such that at the reaction temperature and vacuum theinitiator would be in the absence of the vegetable oil based monomersubstantially evaporated in at most about 120 minutes.
 41. Apolyurethane comprised of the reaction product of a polyisocyanate andthe vegetable based polyol of claim
 1. 42. A polyurethane comprised ofthe reaction product of a polyisocyanate and the vegetable based polyolof claim
 12. 43. A process to make a vegetable based polyol, the processcomprising, i) heating, in the presence of a catalyst a vegetable oilbased monomer having at least one of the formulae:

where m, n, v, r, and s are integers and m is greater than 3, n greaterthan or equal to zero and m+n is from 11 to 19, v is greater than 3, ris greater than or equal to zero, s is greater than or equal to zero andv+r+s is from 10 to 18 until some portion of the VOB monomers havereacted and subsequently ii) introducing an initiator that is a polyol,polyamine, aminoalcohol or mixture thereof to the reacted VOB monomersof step (i) for a time and temperature sufficient to form the vegetablebased polyol under vacuum.
 44. The process of claim 43 wherein theinitiator is volatile at the reaction conditions of step (ii).